Amide resins and resinous vehicles thereof



--moving' by distillation,

Patented Feb. 6, 1951 AMIDE RESIN S AND RESINOUS VEHICLES THEREOF Leonard E. Cadwell, Stamford, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application August 19, 1947, Serial No. 769,541

18 Claims.

. This invention relates to alkylol amides of butendioic-rosin resins, and resinous vehicles thereof suitable for steam-set printing inks. More particularly, this invention is related to amide resins obtained by the distillation-dehydration conversion of the resultant salt obtained by the reaction of butendioic acid-rosin adduct with an alkylol primary amine. Included within the scope of the invention, is the resinous vehicle obtained by dissolving the amide resin in a suitable volatile solvent.

The reaction of hydroxy amines with high acid resins to form resin salts, and the use of these products in steam-set inks is well known in the art. These resins, however, are divided into two general classes, each of which are unsatisfactory for the particular utility of the products of this invention. One group of these prior art resins do not precipitate with steam, and the other group which do precipitate with steam, yield tacky films with poor water resistance. The above disadvantages of the resins of the prior art classes are overcome by this invention, in that these new compositions have improved water tolerance compared with the prior art resins; yet, upon subjection of films from volatile solutions to steam,,the resin is precipitated in a dry tackfree state.

Stated generally, the products of this invention are prepared by dispersing a rosinbutendioic acid adduct in a suitable inert organic solvent, such as xylene, and slowly adding an alkylol primary amine, preferably a monoalkylol primary amine, to the dispersion, while maintaining'at suitable temperature, until complete conversion to the salt is obtained. The temperature is then gradually raised to convert the resulting salt to the corresponding amide, while rethe reaction. water formed. When the theoretical amount of water has been removed, a suitable volatile solvent such as a polyhydric alcohol, and preferably diethylene glycol, may be added to dissolve the amide resin. The inert organic solvent is removed by vacuum distillation to provide the resinous vehicle comprising the volatile solution of the amide resin. In lieu of forming the resinous vehicle, the inertsolvent may be removed therefrom to form the resinous residue, which may be dissolved in the volatile solvent.

-by distillation at 140 It is believed that the invention will be more understood from the following detailed examples given by way of illustration:

Example 1 I I Parts by Weight Maleic acid-rosin adduct 220' Ethanol amine 28.7

Xylene 50 Diethylene glycol l97 The maleic acid-rosin adduct was dissolved in the Xylene, and the ethanol amine added, dropwise thereto, while maintaining the reaction mixture at 130 C. It took approximately 5 minutes to add all of the ethanol amine. Nine and four tenths (9.4) parts of water were then removed C.-152 C. It-took approximately 1 /2 hours to accomplish this distillation. The heat was out 01f and the diethylene glycol added, and the apparatus set up for vacuum distillation to remove the xylene. The xylene was removed by heating at C.- 0., at 45 mm. mercury vacuum. The acid number of this resinous vehicle was 162, the viscositywas Z4, and the Water tolerance was 4.8 cc. of-water per 100 grams of solution. a

Instead of adding thediethylene glycol in-the above example, the xylol could have been removed by vacuum distillation to provide a solid resin having an acid number of 113, and a solidification point of 170.44 C. The viscosity of a 50 solution of this resin in diethylene glycol is Z6, and the viscosity of a 45% solution of thisresin with diethylene glycol is Za-Z4. The resin 'is also infinitely soluble in ethyl alcohol.

Example 2 Parts by weight Water-white gum rosin-maleicacid a-nhy? dride adduct l Glycerol amine 25.7 Xylene 32.0

The rosin-maleic adduct, obtained by reacting 100 parts of rosin and 27.7 parts of maleic anhydride, were dissolved in the xylene, and the glycerol amine added thereto dropwi'se, while maintaining the temperature at C.-l30 C. It took approximately 5 minutes to effect this addition. The reaction mixture was then dehydrated at 120 C.-15 0 C. to remove the water ance of 255 cc. per 100 grams of solution.

Example 3 Parts by weighte- Maleic acid, anhydride-rosin adduct 127.7 2-'amino butanol 25.2 Xylene 32.0

The adduct, which was-*preparedasin' the above Example 2, was disso1ved=in"the-xylene;-

and the 2-amino butanol added dropwise thereto,

while maintaining the temperaturezat$-130 i 01,- 135 C. It took approximately 10 minutes to.-:ei-' feet this addition. Five (5) parts of water were removed by dehydrationat 130 C.-l50C.j' after" which the remaining water was distilled ofi the xyle'ne by?distillation at- 150 0-200 CT, in the presence of a 4 nitrogen atmospheres It 1 required approximately 45 minutes-to remove the water; and approximately 1 hon-rend minutes to remove the xylene.

' Example- 4 Partsby weight Watenwhite' gum. rosin 100/ Fumaric acid 32.8 2" m'eth'yl'e'2 aminopropanol 22.2

Xylene" 30" methylene glycol" 142';

'Iheri rosin? and -:fumaric:.: acid 1 were heated at 200110; foi'islfhoura The xylene :was then added toi zthe resultantadduct to dissolveitit and;iafter solutionlawas? obtained; the; 2'-imethyl'-2 amino propanol-irwas added thereto dropwise, while maintaining reaction mixture at 133 0. 135 C; lt toolc approximately .15 minutes to add "all" of the 2 methyl-2eamincp'ropanolfi The reaction sa1t was them converted to tlie'amide and dehydratedat 135 '=Ci -150 C.; it required approximatelywl hour and lfl' min'utes to efifect this conversion and dehydration; The reactio'n'mix-= tme was then cooled and the -diethylene *glycol added The=apparatus was then set up for-vac unm distillationto-remove the xylene which was removed by -heating at130 0;; and 30 'mm.=vac- Trier-viscosityoi" the "resin solution'- (55% solidsfi wasiZd -and'had a color index of 13:14:-

Eatampleij Partsiby weight Rosin-fumaric acid'adduet 121.3 2eiamit'ioe2emethyl-1,3-propanediol 19.3 X571n8.%2-. 3510 Diet-hylene glycol .112

mately 1 hour to distill ofi 12 parts of water. The reaction mixture was then permitted to cool, and the diethylene glycol was added thereto. The apparatus was set up for vacuum distillation, and xylene removed by distillingat C., and 20 mm. mercury vacuum. The resulting resinous solution had a viscosity of Zq-Za.

Wherein the term acid is used herein, it is intended to include the anhydrides thereof, which may be used interchangeably therefor. By like token, when thejanhyd-ridekis 'usedfithe. acid may be satisfactorily employed as well.

The amide resins and volatile resinous vehicles thereof are particularly applicable in all types ;of;;printingrinkswherein described where drying is'uaccomplished by the application of steam or moisture to printed surfaces. They are particula'rly' useful in printing inks for food wrappers andcontainers', where printing and drying are followed by moisture-proofing. Printing inks preparedzfrom' these resinous vehicles, display muchiimproved stability at high humidities, by virtue of their high water tolerance, yet they are precipitated completely in a dry form upon the addition of more than a critical amount of waterr Iclaimi r l.- A process 'comprising reacting-' a rosin= butendioic acidadduct-with an alliylol primary amine" to" effect the -salt thereof and*heat-'converting said 'salt*to-the corresponding amider 2'; A resinous composition"comprising an alkylol amide; of -rosin-butendioicacid' adduct."

BFA process comprising*-reacting 'a' rosin'-fu-' maric acid' 'adduct" with-"an alkylol primary amine in an inert organic solvent to efiectthesalt-there of, and converting said-salt tothe corresponding amide.

l. A resinous-composition comprising an alkylol amide of rosin-fumaric acid adducti V 5. Aprocess comprising reacting a rosin=maleic acid adductwithan alkylol-primaryemine.in an inert organic 'solventto "effect"formation'tothe salt thereof and converting said salt to. the corre= sponding amide.

6. A resinous composition comprising an alkylol amide" of rosin-maleic acid adduct.

7." A process comprising the: reaction of arr-inert organic solutiOn'ofa rosin'abutendioic acid "adduct with monoethanol' amine, and .conversion ofth'e resultantsalt'to the corresponding amide.

8. A resinous composition comprisingthe' ethe ylol amide. oi rosin-butendioic acid adduct 9. A process comprising'the reactio'n'of an inert organic solution of a rosin-butendioicacidaddu'ct with glycerol. amine and effecting conversion; of the resultant saltitov the corresponding;amide;..-

101A process comprisingthe' reaction of ann'ne ert .organic'. solution of a rosin-butendioic' -acid' adduct withi2-amin'o-2 methyl propanoliandi'fefffecting conversionof "the resultant salt. to the corresponding .amid'e- 111' A process 'comprisingi;thenreaction;ofilan inert organic solution of. a lrosin'ebutendioiciacid' adduct with 2' a1ninoi-2'-'meth'yl.l,SFpropanediOl, andiefiectingmconversion .of resultant-salt to the corresponding-amide.

12." A" process. comprising. thev reaction organ inertorganicisolution of a rosin-butendioic'acid adduct with Z-aminoloutanol, and. 'efi'ctingcom. version of the resultant salt to the corresponding amide.

13. A" resinous vehicle "comprising a highly volatile organic-solvent; and an alkyloliamide' :of' rosin-butendioic adduct di'spersed 'insaid 'solii'enti' 14. A process for preparing a resinous vehicle for printing inks comprising reacting a rosinbutendioic acid adduct with an alkylol primary amine to efiect the salt thereof, converting said salt to the corresponding amide, dehydrating said amide reaction mixture, adding diethylene glycol to said reaction mixture, and removing the inert organic solvent by vacuum distillation.

15. A resinous vehicle comprising a diethylene glycol solution of an ethylol amide of rosinbutendioic acid adduct.

16. A resinous vehicle comprising a diethylene glycol solution of a propanol amide of rosinbutendioic acid adduct.

17. A process comprising reacting a rosinbutendioic acid adduct with a monohydroxy alkylol primary amine to effect the salt thereof, and heat converting said salt to the corresponding amide.

6 18. A process comprising reacting a rosinbutendioic acid adduct with a polyhydroxy alkylol primary amine to effect the salt thereof, and heat converting said salt to the corresponding amide.

LEONARD E. CADWELL.

REFERENCES CITED The following references file of this patent:

UNITED STATES PATENTS are of record in the 

1. A PROCESS COMPRISING REACTING A ROSINBUTENDIOIC ACID ADDUCT WITH AN ALKYLOL PRIMARY AMINE TO EFFECT THE SALT THEREOF, AND HEAT-CONVERTING SAID SALT TO THE CORRESPONDING AMIDE. 